Metalworking lubricant



Patented July 29, 1952 v I 2,605,224 METALWORKING- LUBRICANT Edward Joseph Jahn, Edwards ville ,"Ill., assignor toShell Development Company, San'Francisco; 'Calif., a corporation; of Delaware I 1.

No Drawing. Application June24, 1949,

. Serial No. 101,258

i-gUNITED PATENT OFF-ICE this invention pertains to, metal workin OI.

metal fabrication lubricants for usein rolling. drawing, forging of metals and the like.

Problems encountered in lubricating metals under conditions referred to in the previous paragraph. are particularly complex because of the various factorsencountered such as hightemperature, excess pressure, emulsification, pressure of foreign bodies or contaminants, work speeds and the like. To lubricate effectivelyunder these adverse conditions the lubricant must act primarily as a coolant and. lubricant. ,In the field of rolling lubricants, palm oil was considered most eificient and'suitable'." -However, palm oil has serious drawbacksin that it is diflicult to remove from metal surfaces thereby requiring the use of cleaners which greatly increase operating cost. -Also, it has a tendency to stain surfaces which on annealing mars the surface and exerts a detrimental effect when such metals are to be subsequently-tinned, al-' loyed and the like. In addition metalsurfaces which become too heavily coated with palm oil cause excessive slippage of the rollsthereby de-= creasing rollingv efficiency. Palm oil is also costly, and a cheaper and effective substitute for palm oil as a metal working lubricant is greatly desired. 7

To meet the requirements demanded of agood metal fabricating lubricantsuch as a rolllub-ri cant, it must have high adsorption properties to adhere or wet metal surfaces even in the presence of water. Also enough reductionof friction coefficient must be realized to keep the mill from overheating. 2

Essential properties of such lubricants are: film strength, ability to reduce friction, ability to wet metals in presence of water,-ability to produce a good lustre onmetal surface worked, ease of-removal and non-staining andde-emulsifying properties, i. e., separating from Water and contaminants.

Film strength When lubricated metal surfaces are"forced'to slide past each other under high pressures there is a tendency for surface asperities to penetrate the lubricant film and adhere; this'iin turn permits the transfer of metal'from one surface to another. This phenomenon known. in metalworking, operation as fpick-up, of the worked z'zclainis. (01. 252-405)" Reduction of friction Roll lubricants must possess the ability to reduce friction between therolls and the work sheetin order to reduce power consumption, prevent overheating and minimize the 7 force which must be applied to the rolls, The'property of a lubricant to reduce friction is referredato as oiliness and depends upon the shear strength of the film formed on a metal surface and on the rheological behavior of" thin films of oil when subjected to high pressures.

I I Wettability andadhesion Since roll lubricants are usually used incon junction with water as a coolant, they must possess the property of displacing water-from metal surfaces and resist the washing actionof' large" quantities of 'water'applied to therollsand work sheet. Often washing water is applied in the form of a high-pressure spray so that the ability of thelubricant to adhere to metal surfaces is of paramount importance.

Lustre The appearance of the surface 'of rolled stock. referred to in practice as lustre is markedly influenced by the character of the roll lubricant. To accomplish this, lubricants used for this purpose should be non-staining and prevent microscopic tears on the worked metal surface.

Ease ofrernoval and non-staining A serious drawback of palm oil is the difficulty of removing it from rolled metal sheets. Generally'electrolytic cleaners are required to remove the palm oil for if it is left onthe metal surface and the metal is'thereafter annealed the metal surface becomes stained. "Roll lubricents should, therefore, possess the property of being easily removed when desired and also not stain the surface "with which it is in contact,

regardless of the temperature.

Corrosion Resistant Efficient roll lubricants in L addition. to being able to withstand high temperature and pres- .sure must be non-corrosive during the rolling intervals before being further worked.

It is an object of this invention to provide an improved roll lubricant substantially superior topalm oil. It is another object of this invention to provide a lubricant for metal working which is stable and non-corrosive. Still another object of this invention is to provide a .:1 ing lubricant which tacky metal working lubricant having the property of resisting being displaced by Water sprayed under pressure. Furthermore, it is an object of this invention to provide a metal workcan be easily removed from lubricated surfaces.=

is non staining and which It has now'been discovered that'a .inetal working of lanolin, olein and ocenol. specific types of secondary additives can be admixed into the above blend of acid-treated light oils, e. g. an acid-treated gas oil and fatty materials, said secondary additives being selected from organic amines, alkylated phenolic compounds and salts of organic acids. Thesecondary additives, if used in compositions of this invention, are added in'amounts generally not exceeding 0.01% to 0.5%- by weight. g 7 The light hydrocarbons having a boiling range of from about 300 F. to about 700 F. andzpref erably boiling within the range ofv from about 400 F. to about 650 F. may be acid-treated in'a variety of ways. Thus, such fractions which may be straight-run, thermally and/or catalytically cracked hydrocarbons such asgas oil may betreated with sulfuric acid, or other acids such as phosphoric and hydrochloric-acids or mixtures thereoffollowed by neutralization of separated sour .oil phase by use :of aqueous alkali. The process may be modified bysubjectingtheEacidtreated oil to'a clay treatment; mild oxidation and thelike. "The preferred method of acid-treatingthe base oils used in compositions of'this invention is to acid-treat with 3 to 30 pounds and preferably {iii of this invention are obtained by blendingdnto acid-treated oils as described above, minor amounts of a primary additive selected from the classes including lanolin, olein ;and ,ocenol, the'latter being a technical grade oleyl alcohol. ,If desired, the blends thus obtained may'be'mildly oxidized by either blowing with oxygen or air or allowing the blend to be ex- "posed to the atmosphere for about a week or ten days'at-a temperature of from 135 to 250 F. and preferably at 200 F. a

, Of, the primary additives referred to above, lanolin I and particularly anhydrous lanolin are, most preferred because of its wide applicability in various metal working operations in composi-, tions of this invention. An anhydrous lanolin suitable for use in Compositions of this invention has the following properties: i

Neutralization 'No L 1:48 Iodine N05; -45 Free fatty acid, per cent (AST v I I 1 method B)'i; i 0.74 Water j None operations and particularly. in" cold rolling of aluminum sheets, staining due to I the lubricant used is a serious problem. Although with 6 to 20 pounds of about 87-95% sulfuric acid I per barrel of "oil. The amount and strength of acid used depend upon the base oils source, its boiling range and whether it is a straight run,

thermally cracked or catalytically cracked stock;

For a Mid-Continent or West Texas stock boiling within the gas oil range, between about 6 and about 20 pounds of 93% sulfuric acid is required in order to obtain a desired acid-treated 'oil for metal working.

- The sludge which is formed from the aboveacid treatmentis allowed to settle and is removed. The sour oilis then carefully neutralized with aqueous caustic solution and/or;a lime solution. The aqueous solution is then withdrawn and the oil is then given a clay treatment. Any of the H2SO4/bb1.), neutralized and clay (Attapulgas) treated is given in the table'below: I

'Mid-Cont;

Gas Oil M1d.-Cont.

Gas Oil Gravity API Acid-treated compositions-of this invention reduce staining to a minimum, it has been found that this factor can besubstantiallyentirely eliminated by addition to compositions of this invention minute amountsof metallic naphthenates and/ or oleates or by addition of an alkylated phenol or organic amine. The addition of these secondary additives.

actsasn-excellent stain-suppressors when added in amounts of from 0.01 to 1%; The stain+sup'-- pressors particularly preferred 'are'the Ca, Mg,

Ba, Sr, Cu, Zn, Co, Mn, Al, Pb' naphthenates and/or oleates; the alkylated phenols, e. g. 2,4

dimethyl-S-tertiar'y butyl phenol, 2,4-dibutyl-6- methyl phenol; 2-ethyl-4-octyl phenol; C14" alkylated cardanol, octyl phenol, etc. Among-"the organic amines which can be used-as stain-suppressors are diphenylamine, phenyl-alp'ha-naph thylamine, phenyl-beta-naphthylamine, octyl amine, octadecyl amine, etc. i Specific examples of compositions'of this invention are:

. Per cent Composition A: a v 'Lanolin 4-6' Acid-treated gas oil Balance Composition B: Ocenol 4-6 Acid-treated gas oil Balance Composition C;

Olein 4 6 Acid-treated gas oil Balance Composition D: Oxidized mixture of acidtreated gas oil containing 4-6% lanolin Composition E:

- Lanolin "Ca naphthenate 0.6-0.8 jAcid treated gas oil Balance Composition F: i Lanolin 3-6 Cu naphthenate 0.3 Acid-treated gas oil Balance Composition G: I

Ocenol 3-6 gCa naphthenate 0.6-0.8

Acid-treated gas oil Balance 5 Composition Hz Per cent Theresults-of compositions tested were as 4501: Lanolin r lsl .3-6 xlows: -,a; 2,4 dit'ertbutyl-fi-methylphenol as 0.6-0.8 Composition: Staining rating Acid-treated ga oi1 Balance compositionl v A Composition If 5' Ocenol 1 3-45 I 2,4 ditertbutyl-6-methylphenol 03 0.8 Acid treated g'a's'oil l "'Ba1ance compo-sitiofi'k, 1 taining 5% peanut oil) s i E 'nanoiin" ;s i ;s R's-6 '10 Composition a idated as oil Diphenylar'nine 1' H N qont nine 1% 2, i u 'y1 th Acid-treated gas oil Balance Y P 1) D The alkyl phenol can be ais ersd'inco abut-162% of :1. Composition (add-treated gas l heavy, oil (500 sus at 100 F3 and this mixture is blended cgntajning 10% tetmun) D into the composition. V I -a gas on E The following table further illustrates com- Acid-treated gas i 0 positions of this invention: I In oonjunction with compositions of this in- Lanolmi ea c lA-diteltbutyl-(i-n'ith'yl phen 2,4-dimethyl-6-tertbuty1 phenol octyl phenol Base: I

Acid-treated gas oil Acidgreated hydrocarbon distillate (500- To illustrate the pronounced -improvement obtained from compositions of this invention, ,a number of: these compositions were subjected for test: in the Four-ball weanTester and the compositions were, compared with other-com: ounded rolling lubricants, v

[Condition of test: rotating agents-tan, '1 'ngii'mimmi discs, 'One minute, 680 R. P M 7 'kg-; load; 7o F.] i

Composition Y (gas oil containing 2% lecithin) Composition Z (gas oil containing 5% linseed oil) Compositions of this invention were also sub? jected to the Alcoa Stain test which comprises placing 1 m1. of the material bein'g tested on Ia polished 5"x5" aluminum plate and heatingin' an eleotric'furnace at 650,F.Jior.3'0 minutes. The plate is then examined for staining and'is rated as'follows: l i,

A-s'tain free Blight stain (L-medium stain" D-'-dark medium stain E-dak stain of-other-aclditives can be added, if desired, in order to fortify the compositions:

A. High molecular weight fatty" acids estes v marine oils, e. g.:'

so I

B; Naturally occurring from animal, vegetable, 1. Animal oi1 I Neats-foot Tallow Lard Wool fat: Bone 'Horse toot oils,ietc. 2. Vegetable oils v Castorv Corn Cashew Cottonseed Peanut Kapolc Cocoanut Rapeseed ,Jo'joba Ravison Seed Sesame Olive Sunflower -Kernel palm-oil Teaseed oils, etc. 3i Marine oils- 1 Co dfish 'COdliVEl' I a Dogfish Dolphin body Dolphin fish Herring Japfish Menhaden oils Porpoise body and jaw oils Salmon oil a Sardine andsardine liver oils Seal oil.

-,Sl'iark and shark liv er oils' .l

Spern'iWhale body and e db 's f. 1

' Whale oiijetd j h fatty acidsb'f high mo-f lecular weights: i 1. Saturated- Steario Capric 1 Unde'cylic Arachidic I Laurie Lignoceri'd Myristic fCerolic Palmitic Montanic'acids, etc.

7 Naturally occurring fatty acids of high molecular weights:Continued Y 2.- Unsaturated- Oleic Linoleic I Linoleic Brassidic Erucic Elaidic Substituted fatty acids- Ricinoleic Ricinelaidic Hydroxystearic acids, etc. a I Esters of any of the above acids with mono and polyhydric alcohols and othertypes of esters, e. g.: 1. Glycerol monooleate, methyl dichlorostea- ,rate, diglycol stearate di-2-ethyl hexyl- V azelate diglycol laurate, n-decyl hydrogen phthalate or succinate, octadecyl stearate, polyalkylene glycol esters of monocarboxylic acids. 2. Esters of inorganic acids, e. g. tricresyl phosphate and phosphatidic materials such as cephalin and lecithin. Sulfur-containing materials, e. g.:

Dibenzyl disulfide Sulfurized sperm oil Sulfurized cottonseed oil Sulfurized fatty acids as listed under Halogen-containing materials, e. g.:

Chlorinated paraffin waxes part Chlorinated parafl'in fatty acids and esters e Chlorinated aromatic compounds Chlorinated organic compounds containing sulfur Natural occurring and synthetic waxes Montan Wax Carnauba wax Beeswax Spermaceti Castor oil distillate Ozokerite, etc. I H Polyalkylene glycol polymers, e; Polyethylene glycol and the like.

Rolling lubricants of this invention are well adapted as rust inhibitors after the rolled sheet has been worked.

The roll lubricant of this invention may be applied to the rolls of a sheet metal rolling mill by any suitable means such as spraying, dipping, or the like. It may be applied on the sheet metal prior to, during or after rolling. Preferably the lubricant is warmed to about a temperature of 150 to 175 F. before applying'it to the rolls so as to aid in spreading the lubricant more evenly on the rolls and work piece. 7

In addition to being an excellent rolllubricant, compositions of this invention may be used as drawing lubricants, forging and die lubricants and in various other processes where drawing and working of metals require lubrication.

It is to be understood that while the features of the invention have been described and illustrated in connection with certain specific examples, the invention, however, is not to be limited thereto or otherwise restricted except by theprior art and the scope of the appended claims.

I claim as my invention:

1. A metal working lubricant comprising a sulfuric acid-treated light liquid hydrocarbon having a boiling range of from 300 F. to about 700 F. having incorporated therein from 3 to 10% of a 8 fattyxmaterial selected from the classconsisting of lanolin, oleylalcohol and olein.

2. A metal working lubricant comprising a sulfuric acid-treated light liquid hydrocarbon having a boiling range of from 300 F. to about 700 F. having incorporated therein from 3 to 10% of lanolin. v I H 3. A metalworking lubricant comprising a sulfuric acid-treated liquid hydrocarbon having a boiling range of from 300 F. to about 700 F. having incorporated therein from 3 to- 10% of oleylalcohol.

4. A metal working lubricant comprising a sulfuric acid-treated light liquid hydrocarbon having a boiling range of from 300 F. to about 700 F. having incorporated therein from- 3 to 10% of olein.

5. Ametal working lubricant consisting essen- .tially of a major amount of gas oil which has been acid treated with. from 6 to20 pounds of 37-95% sulfuric acid per barrel of gas oil from 3 to 10% of a fatty material selected from the class consisting of lanolin, oleyl alcohol, and olein.

6. A metal working lubricant consisting essentially of a major amount of an oxidized gas oil which has been acid treated with from 6 to 20 pounds of 87-95% sulfuric acid per barrel of gas oil and from 3 to 10% of a fatty material selected from the class consisting of lanolin, olein and oleyl alcohol.

7. A metal working lubricant comprising gas oil which has been acid treated with from 6 to "20 pounds of 87-95% sulfuric acid per barrel-0f oiliand having incorporated therein from 3 to 10% of olein. v p 2 I p .10., A metal working lubricant comprising an oxidized gas oil which has been acid treated with from 6 to 20 pounds of 87-95% sulfuric ,acidper barrel of oil and having incorporated therein from 3 to 10% of lanolin.

ll. A metal working lubricant comprisingan oxidized gas oil which has been acid treated with from 6 to 20pounds of 87-95% sulfuric acid per barrel of oil and having incorporated therein from 3 to 10% of oleyl alcohol.

12. A metal working lubricant comprising an oxidized gas oil which ha :been acid treated with from 6 to 20 pounds or 87-95% sulfuric acid per barrel of oil and having, incorporated therein from 3 to 10% of olein.

13. A metal working lubricant consisting essentially of a major amount of a gas oil which has been acid treated withv about 20. pounds of 93% sulfuric acid per barrel of gasoil and from 3 ,to 10% of a fatty material selected from the class consisting of lanolin, oleylalcohol and olein and from 0.01 to 1% of anoil-soluble polyalkyl phenol;

9 15. A metal working lubricant comprising the following ingredients in the following proportions:

Per cent Lanolin 4-6 Acid-treated gas oil in accordance with claim 13 96-94 16. A metal working lubricant comprising the following ingredients in the following proportions:

Per cent Oleyl alcohol 4-6 Acid-treated gas oil in accordance with claim 13 96-94 17. A metal working lubricant comprising the following ingredients in the following proportions:

Per cent Olein 4-6 Acid-treated gas oil in accordance with claim 96-94 18. A metal working lubricant consisting essentially of the following ingredients in the following proportions:

Per cent Lanolin 3-6 Ca naphthenate 0.6-0.8

Acid treated gas oil in accordance with claim 1 Balance 19. A metal working lubricant consisting essentially of the following ingredients in the following proportions:

Per cent Oleyl alc 3-6 Ca naphthenate 0.6-0.8 Acid treated gas oil in accordance with claim 13 Balance 20. A metal working lubricant consisting essentially of the following ingredients in the following proportions:

Per cent Lanolin 3-6 2,4 ditertbutyl-G-methylphenol 0.6-0.8

Acid treated gas OH in accordance with claim 13 Balance 21. A metal working lubricant consisting essentially of the following ingredients in the following proportions:

. Per cent Oleylalcohol 3-6 2,4 ditertbutyl-S-methylphenol 0.6-0.8

' Acid treated gas oil in accordance with claim 13 Balance 22. A metal working lubricant consisting essentially of the following ingredients in the following proportions:

Per cent Lanolin 3-6 Diphenylamine 0.6-0.8 Acid treated gas oil in accordance with claim 13 Balance EDWARD JOSEPH JAHN.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,936,583 Clapp Nov, 28, 1933 2,151,285 Toussaint Mar. 21, 1939 2,151,353 Montgomery Mar. 21, 1939 2,153,811 Montgomery Apr. 11, 1939 2,202,825 Brandes June 4, 1940 2,202,877 Stevens June 4, 1940 2,256,603 Wright Sept. 23, 1941 2,403,288 Rosenstiehl July 2, 1946 2,472,503 Minne June 7, 1949 OTHER, REFERENCES Vol. 1, Mattiello, Protective and Decorative Coatings, 1941, pp. 576, 577 and 578. 

1. A METAL WORKING LUBRICANT COMPRISING A SULFURIC ACID-TREATED LIGHT LIQUID HYDROCARBON HAVING A BOILING RANGE OF FROM 300* F. TO ABOUT 700* F. HAVING INCORPORATED THEREIN FROM 3 TO 10% OF A FATTY MATERIAL SELECTED FROM THE CLASS CONSISTING OF LANOLIN, OLEYL ALCOHOL AND OLEIN. 